Influence of amorphous alkaline lignin on the crystallization behavior and thermal properties of bacterial polyester

Bacterial polyester poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and alkaline lignin composites were prepared via melt processing method, and the influence of amorphous lignin on the crystallization behavior and thermal properties of PHBV were investigated. It was found that dual melting peaks appeared in DSC curves of PHBV/lignin composites, while only one single peak existed in PHBV. The non‐isothermal crystallization process analyzed by Jeziorny method suggested that lignin changed the nucleation mode of composites and hindered the crystallization rate of PHBV. Data calculated from the results of WAXD demonstrated that lignin did not change the basic crystal structure of PHBV, but decreased the average size of the lamellar stacks. POM results confirmed that the effect of lignin on the crystallization behavior of PHBV carried out in two opposite way, namely the enhanced effect of nucleation and the hindered effect of growth. Besides, the thermal stability of composites was also decreased significantly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41325.     

木质素基PF泡沫的发泡工艺与性能

利用低廉的木质素部分取代苯酚制备木质素基酚醛树脂(PF)泡沫,采用正交试验对木质素基PF发泡工艺进行了研究,研究了表面活性剂(吐温–80)用量、发泡剂(正戊烷)用量、发泡温度三个因素对木质素基PF泡沫性能的影响,从而优化发泡工艺。实验结果表明,对木质素基PF泡沫的极限氧指数(LOI)和导热系数影响最大的是发泡温度,而对于压缩强度影响最大的是表面活性剂用量。木质素基PF泡沫的最佳发泡工艺为:表面活性剂(吐温–80)用量为8%、发泡剂(正戊烷)用量为12%,发泡温度为90℃,所得泡沫具有较好的热稳定性,其LOI为39%,压缩强度为0.32 MPa,导热系数为0.025 W/(m·K)。     

Parameters Affecting the Cross-Flow Filtration of Dissolved LignoBoost Kraft Lignin

In the kraft pulping process, the lignin-containing by-product kraft black liquor is currently combusted as an energy source. LignoBoost is a technique that extracts lignin from kraft black liquor, resulting in a lignin-lean black liquor, which is returned to the process, and an extracted kraft lignin. To facilitate the use of the extracted kraft lignin in high-value applications, it can be refined via fractionation to produce a more homogeneous starting raw material. Hence, the aim of this study is to investigate the behavior of dissolved softwood kraft lignin during cross-flow filtration. The effects of the lignin concentration, pH, and ionic strength on the fractionation of the dissolved lignin during cross-flow filtration are investigated. The results indicate that large amounts of low-molecular-weight kraft lignin can be produced from solutions having a low lignin concentration. Furthermore, the effects of pH and ionic strength on the fractionation of low-molecular-weight lignin are identified within the studied ranges.     

Purification of Biorefinery Lignin with Alcohols

After hydrothermal pretreatment and enzymatic hydrolysis of wheat straw, a slurry rich in lignin but with a high content of inorganic substances, especially silica, and residual carbohydrates is produced. This slurry was used to develop an ethanol organosolv separation method to produce silica-free lignin fractions. The addition of para toluene sulphonic acid (PTSA) and the use of two alternative long-chain alcohols, oleyl alcohol or nonylphenol, were tested. In every reaction, two lignin fractions were produced and their molecular size and elemental composition were characterized. The yield of each fraction and the change in MWD were studied as a function of temperature and solid to liquid ratio. At 100, 150, and 200°C and with the use of PTSA, high-purity lignin fractions were obtained. After lignin fractionation with nonylphenol, a liquid silica-free product with high lignin content was obtained in yields between 17 and 72%.     

木质素荧光研究进展

木质素是植物细胞壁荧光的主要来源,是一种天然高分子荧光材料,但木质素的荧光机理和调控机制不明确,制约了其荧光特性的高值利用。本文从木质素荧光团化学结构的筛选和木质素荧光团间聚集耦合态的研究两方面出发,系统地综述了木质素荧光的研究现状,并分别对其研究思路和存在的科学问题进行了总结和凝练。分析表明,首先,由于木质素的自吸收效应和荧光淬灭剂的存在,仅从荧光强度和发射波长两方面筛选与真实木质素荧光相近的模型物作为其荧光团的结论存在一定局限性;其次,木质素荧光团间存在相互作用,单独分析木质素荧光团的化学结构意义有限,木质素真实发光基团是这些荧光团间的聚集耦合态;再次,在木质素微结构聚集行为研究和聚集诱导发光理论的基础上,已从宏观层面明确了木质素胶团间和胶团内两种基本聚集行为对其荧光的影响规律和作用机制,今后的研究应完善木质素聚集荧光行为的关联模型,并从微观分子层面深入揭示木质素荧光团间的耦合机制;最后,木质素荧光并非是一个单纯的光物理性质研究,更是一个由木质素化学结构解析、木质素微结构调控、木质素激发态能量转移等多方向交叉形成的综合性课题,揭示木质素荧光机制仍然是一个具有挑战性的工作,进而会对木质素其他方向的研究起到促进作用。     

纳米木质素基多孔炭的制备及其电化学性能

基于绿色低共熔溶剂（DES）高效分离麦草生物质组分以制备纳米木质素（LNP）,本文采用化学活化法并进一步热解炭化制备纳米木质素基多孔炭（LNPC）。借助SEM、Raman、BET-物理吸附等分析手段研究了锌系活化剂及热解炭化温度（600℃、700℃、800℃）对LNPC的结构特征及电化学性能的影响。研究结果表明,相对于LNP直接热解炭化后纳米碳粒子的极易团聚,经锌化物活化后所制备的LNPC表现出更好的分散性和多级孔道形貌结构。尤其,以ZnCO₃活化后制备的LNPC-ZnCO₃-800具有更突出的性能,较高石墨化程度（I_D/I_G为0.68）、较高BET比表面积（679m²/g）、高介孔率（86.7%）、均匀纳米碳粒子构成的介孔结构。此外,以LNPC-ZnCO₃-800制备的工作电极,在0.5A/g时的比电容可达179F/g,与直接热解炭化的LNPC-800（64F/g）相比,其比电容的容量提高了180%。     

制备条件对生物炭载铁催化剂催化破络Ni-EDTA性能及活性组分浸出的影响

为加强木质素高值化利用,以木质素和铁盐为原料,采用共热解法制备木质素生物炭载铁催化剂。考察铁源前体类型、铁负载量、升温速率和热解温度等制备条件对催化剂催化破络Ni-乙二胺四乙酸（EDTA）性能和铁活性组分浸出的影响,并结合不同热解温度下催化剂孔隙结构、表面元素及晶体结构等表征分析,系统阐述热解温度对催化剂性能的影响机制。结果表明,铁源前体类型直接决定催化剂表面元素组成、极性及Fe活性组分分布情况,以硝酸铁为铁源前体时催化剂性能最佳。负载铁活性物种有助于增加催化剂表面活性位点数量,升温速率可以改变生物炭孔隙结构,热解温度则决定生物炭碳质结构的形成及对Fe活性组分的固载能力。随着热解温度的升高,Fe活性组分逐渐向催化剂内部迁移,600℃时Fe浸出量始终低于1.0mg/L,催化氧化过程由均相Fenton反应为主向非均相反应转变;与此同时,催化剂表面O、N、S活性位点减少,其共同作用致使催化剂失活和Ni-EDTA破络效果降低。上述结果为以木质素生物炭为催化剂载体设计与制备提供了基础数据。     

离子液体中木质素的酯化及其对环氧树脂的改性

以麦草醇解木质素为原料,丁二酸酐(SA)为酯化剂,1-丁基-3-甲基咪唑氯盐离子液体为反应介质,在不添加其他反应助剂和催化剂的条件下,对木质素进行酯化改性,制备了酯化木质素。研究了温度、时间、n(SA)/n(—OH)等对酯化木质素接枝率的影响,并探讨了酯化木质素对环氧树脂(EP)热稳定性、耐热性能、弯曲应力及黏接性能的影响。结果表明:酯化木质素的接枝率随n(SA)/n(—OH)增大而提高,当酯化反应在80℃持续2.0 h时,接枝率高达68%;酯化木质素中出现明显的酯基特征峰,且其热稳定性得到改善;加入酯化木质素使EP的热稳定性得到改善,维卡软化温度提高近5.0℃,弯曲应力和拉伸剪切强度均有所增加。     

环保型聚碳酸亚丙酯复合调湿材料的性能研究

以溶液共混法将聚碳酸亚丙酯(PPC)、木质素、沸石、硅藻土制得复合材料,测试复合材料的吸放湿性能。结果表明:无机调湿材料吸放湿速度快,但湿容量小;有机调湿材料吸放湿速度中等或较慢,但湿容量大。而通过复合无机与有机调湿材料料,可以得到吸放湿速度快且湿容量大的调湿材料。     

球形木质素珠体接枝丙烯腈的影响因素研究

利用反相悬浮聚合技术制备球形木质素珠体,再以Fe2＋/H202为引发体系,采用正交实验综合研究了球形木质素珠体与丙烯腈的接枝共聚反应的各种影响因素对珠体的接枝率和接枝效率的影响。结果表明：当m（单体）／m（基体）=10：1,反应时间为90min,反应温度55℃,Fe2＋浓度为0．03mmol／L,H202浓度为2．97mmol／L时,可以得到最佳的接枝率和较高的接枝效率,木质素一丙烯腈接枝共聚物的接枝率为780％,接枝效率可达76．0％。